Norbornene-type polymers having quaternary ammonium functionality

ABSTRACT

Embodiments of the present disclosure encompass vinyl addition and ROMP polymers having at least one type of repeating unit that encompasses a comprise N + (CH 3 ) 3 OH −  moiety. Other embodiments in accordance with the disclosure include alkali anion-exchange membranes (AAEMs) made from one of such polymers, anion fuel cells (AFCs) that encompass such AAEMs and components of such AFCs, other than the AAEM, that encompass one of such polymers.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of, is entitled to and claimspriority under 35 U.S.C. §120 to U.S. non-provisional patent applicationSer. No. 12/966,768, filed Dec. 13, 2010, which is entitled to andclaims priority to U.S. provisional application both entitled,“Norbornene-Type Polymers Having Quaternary Ammonium Functionality”,having Ser. No. 61/238,994, filed Dec. 11, 2009, which are bothincorporated herein by reference in their entirety.

TECHNICAL FIELD

Embodiments of the present disclosure relate generally tonorbornene-type polymers having quaternary ammonium functionality andmore specifically to norbornene-type vinyl addition and ROMP polymersuseful for forming hydroxide-ionconducting alkali anion-exchangemembranes (AAEMs) and alkali fuel cells (AFCs) encompassing a firstelectrode, an AAEM and a second electrode, where each electrode's activelayer is in contact with the AAEM.

BACKGROUND

Alkaline fuel cells (AFCs) are one of the most developed technologiesand have been used since the mid-1960s by NASA in the Apollo and SpaceShuttle programs. The fuel cells on board these spacecraft providedelectrical power for on-board systems, as well as drinking water andwere selected because they are among the most efficient in generatingelectricity having an efficiency reaching almost 70%.

The NASA AFCs used an aqueous electrolyte, specifically a solution ofpotassium hydroxide (KOH) retained in a porous stabilized matrix. Thecharge carrier for an AFC is the hydroxyl ion (OH⁻) that migrates fromthe cathode to the anode where they react with hydrogen to produce waterand electrons. The water formed at the anode migrates back to thecathode to regenerate hydroxyl ions. The entire set of reactions isthen:

Anode Reaction: 2 H₂+4 OH⁻=>4 H₂O+4e ⁻

Cathode Reaction: O₂+2H₂O+4e ⁻=>4OH⁻

Overall Net Reaction: 2H₂+O₂=>2H₂O

Despite their high efficiency, reasonable operating temperatures andother positive attributes, the NASA AFCs were very sensitive to CO₂ thatis likely to be present in the fuel used by the cell or environmentally.This sensitivity comes from even trace amounts of CO₂, CO, H₂O and CH₄reacting with the KOH electrolyte, poisoning it rapidly, and severelydegrading the fuel cell performance by either the dilution of theelectrolyte or the formation of carbonates that reduce the electrolyte'spH and hence the kinetics of the electrochemical reactions at the levelof the electrodes, impairing their performance. Therefore, such AFCswere limited to closed environments, such as space and underseavehicles, running on pure hydrogen and oxygen can be worthwhile.

On the positive side, and in addition to their high efficiency and lowoperating temperature, AFCs are the cheapest fuel cells to manufactureas the catalyst that is required on the electrodes can be any of anumber of different materials that are relatively inexpensive comparedto the noble catalysts required for other types of fuel cells.Therefore, there has been considerable interest in solving theirsensitivity to poisoning, in a manner other than providing pure orcleansed hydrogen and oxygen, and take advantage of the AFCs positiveattributes such as operation at relatively low temperatures and highefficiency to provide a quick starting power source and high fuelefficiency, respectively.

In recent years, interest has grown in the development of anion exchangemembranes (AEMs) for use in AFCs and electrolyzers due to the lowoverpotentials associated with many electrochemical reactions at high pHand the potential to forego noble metal catalysts. AEMs serve as aninteresting counterpoint to the more widely developed and understoodproton or cation exchange membranes (PEM or CEM). However, there are noreadily available anion exchange membranes that serve as a commercialstandard for electrochemical applications such as DuPont's Nafion® PSFA(perfluorosulfonic acid) membranes do in the field of cation exchangemembranes.

The use of anionic fuel cells based on solid polymeric anion exchangemembranes (AEMs) have been demonstrated and their use in both AFCs andalkaline-membrane DMFCs (direct methanol fuel cells). Further, the usemetal-free anion exchange membranes operating at elevated pH potentiallylowers or eliminates the need for noble metal based catalysts andimproves the kinetics of the electrochemical reactions. There areadditional advantages to AEMs, and in particular to polymeric alkalianion exchange membranes (AAEMs). For example, it is likely thatelectrode construction and orientation limitations can be overcome forAAEMs as the conducting species would be incorporated into the fixedsolid polymer AAEM. Additionally, even though some CO₃-2/HCO₃-formationat the anode is likely to occur, there are no mobile cations (Na+ or K+)present in the AAEM to precipitate solid crystals of metal carbonate toblock or destroy the electrode layers since with AAEMs the cations areimmobilized. Further, as there is no liquid caustic electrolyte present,electrode weeping and component corrosion should be minimized.

Therefore there is a need for AAEMs that have the necessaryconductivity, resistance to water swelling, mechanical strength, andchemical stability at operating temperatures to provide the nextgeneration of AFCs.

DETAILED DESCRIPTION

As previously mentioned, chemical stability, with respect to thecationic groups attached to the membrane, at operating temperatures is aproperty that is an area of focus focus in developing new AAEMs for fuelcells. If one were to consider an electrochemical cell without any addedelectrolyte, the localized pH within the ion-conducting channels of themembrane will be quite high. Also, while an AFC does does not requireoperating temperatures as high as what is required for fuel cellsencompassing proton exchange membranes (PEMs) to achieve adequatereaction kinetics, AFCs can also benefit from operation at elevatedtemperatures as it is expected expected that such elevated temperaturescan enhance hydroxyl transport and thus enhance fuel cell performance.However, the combination of high pH and elevated temperature can lead tochemical attack on the quaternary ammonium groups, most commonly byeither an E2 (Hofmann degradation) mechanism or by an SN2 substitutionsubstitution reaction. The elimination reaction pathway can be avoidedby using quaternary ammonium groups that do not have β-hydrogens, suchas the benzyltrimethylammonium group. The substitution pathway cannot beavoided so easily, and several approaches have been tried to reduce thesusceptibility of the ammonium group to the substitution reaction.

Many anion exchange polymers employ quaternary ammonium groups attachedto a hydrocarbon polymer backbone, and most recently, ammoniumfunctionalized norbornene-type monomers were incorporated directly via aring-opening metathesis polymerization (ROMP) route withdicyclopentadiene to form what is reported as mechanically strong AAEMswith high hydroxide ion conductivities and exceptional methanoltolerance, G. W. Coates et al. J. Am. Chem. Soc. 2009, 131, 12888-12889(Coates I). With this method, Coates I uses the air-stable Grubbs'second generation catalyst (Ru) which enables functionalized monomers tobe polymerized, R. H. Grubbs et al., Handbook of Metathesis, Ed.:Wiley-VCH, Weinheim, Germany, 2003, R. H. Grubbs et al., Acc. Chem. Res.2001, 34, 18-29, R. H. Grubbs et al., Angew. Chem. Int. Ed., 2006, 45,3760-3765. However, ROMP copolymers of Coates I (shown below), havingunsaturated C to C bonds are known to be less oxidatively stable thananalogous vinyl addition polymers (Aps) that are free of suchunsaturation.

Further, while Coates I report that the thickness and properties offilms made from non-hydrogenated ROMP polymers can be easily controlledby varying the amount and ratios of their Structure 1 todicyclopentadiene (ibid. p. 12888) they also reported that the range ofsuch variations was limited as a film with ratio greater than 1:1(Structure 1: DCPD) demonstrated swelling and hydrogel formation, whilefilms having the inverse ratio were not sufficiently conductive (ibid.p. 12888-12889).

Because of the exceptional functional group tolerance of Grubbs' secondgeneration catalyst, the synthetic method of Coates I eliminated theneed for post-polymerization modification, thereby allowing the facilesynthesis of highly conductive and mechanically strong AAEMs. However,because of the cross-linked nature of the AAEMs, they are insoluble inall solvents limiting their utility. Thus, there there is a general needto develop non-cross-linked polymers that can offer benefits such suchas (i) solvent processability, (ii) film generation, (iii) secondaryfilm treatment, such as functionalization and crosslinking, and (iv)chemical tunability. In accordance accordance with the presentdisclosure, in contrast with that disclosed by Coates,tetraalkylammoniumfunctionalized polynorbornenes are solvent processableand can be be used as an AAEM. Further as such, addition polymerizedpolymers lack β-hydrogen β-hydrogen atom degradation from Hoffmannelimination in the hydroxide form, thus increasing the hydroxidestability over what is reported in Coates. It is also known that thatthe trimethylammonium groups have been shown to be reasonably stable,exhibiting exhibiting negligible degradation under alkaline conditionsat elevated temperatures when properly hydrated.

The addition polymerized norbornene polymers described herein are ofinterest for the synthesis of highly conductive and solvent processabletetraalkylammoniumfunctionalized polynorbornenes for use as an AAEM andas saturated polymers further impart oxidative stability compared toROMP polymers. Additionally, the lack of β-hydrogen atoms in the AP AAEMprevents Hofmann elimination degradation from occurring in the hydroxideform, increasing the ammonium ion stability. It is also known that thetrimethylammonium groups have been shown to be reasonably stable,exhibiting negligible degradation under alkaline conditions at elevatedtemperatures when properly hydrated.

It has also been reported by Chempath et al. in J. Phys. Chem. C, 2008,112, 3179-3182 and Einsla et al. in ECS Transactions, 11(1) 1173-1180(2007) that tetraalkylammonium-based cations show reasonable stabilityin alkaline media, i.e., benzyltrimethylammonium hydroxides displayedmuch better stability than the phenyltrimethylammonium hydroxides undersimilar conditions. Specifically it was reported that solutions ofbenzyltrimethylammonium cation in 1N, 3N and 5N sodium hydroxide showedlittle degradation after being held at 80° C. for 29 days (Einsla etal., FIG. 4, and p. 1179). Einsla et al. also explored the effect ofhydration on cation stability by preparing solutions of thebenzyltrimethylammonium cation in ammonium ammonium hydroxide toeliminate the presence of any sodium cations. Here sealed solutionsheated to 120° C. showed more significant degradation in 48 hours thanseen in in the 29 day study. Einsla et al., suggested that solvation ofOH⁻ anions was important important for the stability of the head groups(ibid. p. 1178 and FIG. 5, p. 1179). Therefore it is believed likelythat membrane conditions that lead to good solvation will will providegreater stability of the cations than those that lead to poor solvation.

Recently, G. W. Coates et al., J. Am. Chem. Soc. 2010, 132, 3400-3404(Coates II), reported the use of tetraalkylammonium-functionalizedcross-linkers, rather than the DCPD used in Coates I, as such newcross-linkers were found not to detract from ion concentration and thusconductivity of the material (ibid. p. 3400). In particular, Coates IIis directed to the use of Compound 1:

as a comonomer of cyclooctene (COE) to directly form the cross-linkedpolymer:

However, as was observed above for Coates I, the resulting ROMP polymerof Coates II is also unsaturated. Since the ROMP polymerization ofnorbornene results in in an unsaturated polymer, removal of theunsaturation leads to an additional step. Furthermore, ROMP polymershaving double bonds in their backbones leads to poor thermo-oxidativestability. This shortcoming can be overcome through hydrogenation, whichcan modify other properties of the polymers as well. (see Register etal. in Macromol. Rapid Commun. 2008, 29, 713-718) It is clear that thepolymer of Coates I I will be less oxidatively stable than ahydrogenated ROMP polymer or a saturated polymer resulting from a vinyladdition polymerization.

Thus believing that norbornene-type polymers formed by vinyl additionpolymerization or by ROMP polymerization of two or more types ofnorbornene-type monomers, followed by hydrogenation, would provide moreoxidatively stable polymers than reported by either Coates I or II, aswell as providing additional flexibility in tailoring the polymer'sconductive, chemical and physical properties, the polymer embodiments inaccordance with the present disclosure encompass both norbornene-typevinyl addition polymers and hydrogenated norbornene-type ROMP polymerswhere the latter exclude copolymers of DCPD or cyclootene.

To this effect, some hydrogenated ROMP polymer embodiments of thepresent disclosure are hydroxide ion conducting polymers derived fromtwo or more norbornene-type monomers where a first such monomer isrepresented by Formula I and a second such monomer is represented byFormula II, both shown below:

where for Formula I, m is from 0 to 3, at least one of R₁, R₂, R₃ and R₄is the pendent group represented by Formula III (alternately referred toas QAS for quaternary quaternary ammonium salt) and the others areindependently a hydrogen, a C₁ to C₁₀ alkyl, an aryl or an alkyl-arylgroup. For Formula II, m is as defined above and at least one of R₅, R₆,R₇ and R₈ is a substituted or unsubstituted maleimide-alkyl pendentgroup group where the alkyl is a C₁ to C₆ alkyl or other cross-linkablegroups such as NB-ether-NB (e.g., NBCH₂OCH₂NB, NBCH₂(OCH₂CH₂)₂OCH2NB,and NBCH₂(OCH₂CH₂)₃OCH₂NB), NB-alkylene-NB (e.g., NB-NB, NB-Et-NB,NB-Bu-NB, and NB-Hx-NB); NB-aryl-NB (e.g., NBC₆H₄NB and NBCH₂C₆H₄CH₂NB),and the others are independently selected from a hydrogen, a C₁ C₁ toC₁₂ alkyl, a terminally halogenated alkyl, an alkyl-aryl where the arylportion is optionally halogenated or a methyl glycol ether such as—CH₂—(OCH₂CH₂)_(q)—OMe where where q is from 1 to 4. For Formula III, R′is selected from —(CH₂)_(p)—, where p is from 0 0 to 12; Ar is anoptional aromatic group having one or more aromatic rings; R″ isselected from —(CH₂)_(p)— where p is from 0 to 12, or—(CH₂)_(s)—O—(CH₂)_(t)—, where s and t are are independently from 1 to6, and R″ is coupled to the nitrogen of the quaternary ammoniumfunctional group by a covalent bond, each of R_(a), R_(b) and R_(c) areindependently selected from a methyl, an aryl or alkyl-aryl group wherethe alkyl is a C₁ C₁ to C₄ alkyl, and v is either 1 or 2. Thus, in eachROMP polymer derived from the above monomers, there is a first type ofnorbornene-type repeating unit that encompasses a QAS group and a secondrepeating unit that encompasses a substituted or or unsubstitutedmaleimide-alkyl pendent group or one of the aforementioned othercross-linkable pendent groups.

With regard to vinyl addition polymer embodiments in accordance with thepresent disclosure, such are also hydroxide ion conducting polymersderived from two or more norbornene-type monomers where a first suchmonomer is represented by Formula A and a second such monomer isrepresented by Formula B, both shown below:

For Formula A, m is from 0 to 3, at least one of R₉, R₁₀, R₁₁ and R₁₂ isa functional group (FG) capable of quaternization, as discussed below,and the others are independently a hydrogen, a C₁ to C₅ alkyl, an arylor an alkyl-aryl group. For Formula B, m is as defined above and atleast one of R₁₃, R₁₄, R₁₅ and R₁₆ is a substituted or unsubstitutedmaleimide-alkyl pendent group where the alkyl is a C₁ to C₄ alkyl oranother cross-linkable group, as described above, and the others areindependently selected from a hydrogen, a C₁ to C₁₂ alkyl, an alkyl-arylor a methyl glycol ether such as -CH₂-(OCH₂CH₂)_(q)-OMe where q is from1 to 4.

Exemplary monomers in accordance with Formula I include, but are notlimited to:

With respect to monomers in accordance Formula A, the above monomerswhile not directly polymerizable via vinyl addition polymerization, canbe made available by post-polymerization functionalization.Additionally, it is believed that monomers that incorporate a quaternaryamine such as those represented by general formulae IVa below, as wellas the specific examples for each general formula that follow inexemplary formulae IVb, are suitable for embodiments in accordance withthe present disclosure. Such pendent groups include:

With regard to the polymerization of the above and below monomers,exemplary ROMP polymerization processes employing Ru and Os transitionmetal initiators are described in U.S. Pat. No. 6,838,489, which isincorporated herein by reference in its entirety; and exemplary vinyladdition polymerization processes employing Group VIII transition metalcatalysts are described in US 2006/0020068 A1, which is incorporatedherein by reference in its entirety.

Both the ROMP and vinyl addition polymer embodiments of the presentdisclosure are formed having a weight average molecular weight (Mw) thatis appropriate to their use. Generally, a Mw from 5,000 to 500,000 isfound appropriate for some embodiments, while for other embodimentsother Mw ranges can be advantageous. For example, for some embodiments,it is advantageous for the polymer to have a Mw from at least 30,000,while in others from at least 60,000. In some embodiments, the upperrange of the polymer's Mw is up to 400,000, while in others is up to250,000. It will be understood that since an appropriate Mw is afunction of the desired physical properties in the anionic polymermembrane formed therefrom, it is a design choice and thus any Mw withinthe ranges provided above is within the scope of the present disclosure.

While some ROMP polymer embodiments of the present disclosure can beformed formed directly from a monomer having an ammonium cation pendentgroup in accordance with Formula III, where a saturated polymer isdesired, monomers in accordance with Formulae A and B can be contactedwith a ring-opening metathesis polymerization (ROMP) initiator and theresultant unsaturated polymer hydrogenated to to a saturated polymer.This ring-opening metathesis polymerization can be accomplished ineither in solution or as 100% reactive solids that is to say as a masspolymerization with little or no solvents. The following schemeexemplifies the hydrogenation of the ring-opened metathesized polymer(ROMP) followed by conversion of an aryl-alkyl halide pendent group to aquaternary ammonium salt (see the the following reaction sequence ofreactions 1 (polymerization), 2 (hydrogenation), 3 (quaternization), and4 (chloride to hydroxide metathesis)).

It should be understood, of course, that where an unsaturated ROMPpolymer is desired, only Reaction 1 of the above scheme need beperformed provided that the starting monomer is in accordance withFormula I. Such reaction sequence is as shown below:

For polymer embodiments in accordance with forming a vinyl additionpolymer, generally a monomer having a pendent functional group that canbe quarternarized, for example an aryl-alkyl halide such as in the aboveFormula IV, the reaction scheme illustrated below is generally employed.

Since, it is believed that the base stability of quaternary aminependent groups improves as the aliphatic chain length of the alkylsubstituent increases, and further as it it is believed thatincorporating repeating units into a polymer with two or more quaternaryamine cations allows more freedom in the selection of other repeatingunits units that will allow for the tailoring of polymer propertieswhile maintaining high conductivity. Thus, unlike the limited range ofmonomer ratios reported in Coates I with with a DPCD copolymer, or theslightly less limited range of monomer ratios reported in in Coates IIwith a COE copolymer, the above vinyl addition plus postfunctionalization functionalization scheme of some embodiments of thecurrent disclosure can provide for for the inclusion of monomers presentin an amount sufficient to address swelling in hot hot methanol, ionexchange capacity (IEC), polymer stability, and mechanical strengthstrength without decreasing hydroxide ion conductivity. For example,such polymers can incorporate a higher ratio of cross-linking repeatingunits where repeating units containing quaternary ammonium moieties arepolyfunctional. Additionally, improvements in membrane stability underalkaline conditions can be accomplished by by the incorporation oftrimethylammonium groups in structures which do not possess —-hydrogenatoms, thereby preventing degradation by Hofmann elimination. Stillfurther, as a design option, functionalized tetracyclododecene (TDFG)monomeric units units may be incorporated into the polymer backbone toeffect changes in mechanical, thermal, and transport properties

Exemplary repeating units that are available from the above vinylpolymerization scheme include, but are not limited to, the following:

Further to the vinyl addition polymerization plus post-functionalizationscheme, the initial monomer can be, for example NBPhCH₂X (where X isselected from Cl, Br, or or I). That is to say that the functional groupof that first type of monomer is an aryl-halogenated-alkyl. Thispolymerization can be performed in solution employing a a nickelinitiator/catalyst Ni(Toluene)(C₆F₅)₂ or an in-situ generated nickelinitiator/catalyst) or a palladium catalyst, such as[Pd(P-i-Pr₃)₂(NCCH₃)(OAc)][B(C₆F₅)₄] or [Pd(PCy₃)₂(NCCH₃)(H)][B(C₆F₅)₄]or an in-situ generated palladium catalyst) to generate the saturatedpolymer shown. Quaternization of these halogenated groups can beeffected through appropriate contacting with trimethylamine (N(CH₃)₃)(e.g., immersing in a solution of 40-75% trimethylamine at roomtemperature for a time sufficient to result in the desired degree degreeof amination). That is to say that the halogen of the pendent group isreplaced by by the quaternary ammonium function N⁺(CH₃)₃ and a halogencounter-ion which is replaced by a hydroxide ion.

Still further to the vinyl addition polymerization pluspost-functionalization scheme, monomers having a particular exo- orendo-configuration can be polymerized to form repeating units thatretain the original configuration, see the exemplary repeating unitsprovided below. It should be understood that through the use of suchconfiguration specific monomers, some physical and chemical propertiesof the resulting polymers can be altered from that which would beprovided if the diastereomeric mixture of such monomers has beenemployed.

The norbornene monomers useful for the preparation of the quaternaryammonium ammonium containing vinyl polymerized polynorbornenes can begenerated, as exemplified below, by the (i) Diels-Alder reaction ofcyclopentadiene and α,ω-halogen α,ω-halogen olefins, those containing aterminal olefin and a terminal halogen, such as as 4-chloro-1-butene,chloromethylstyrene, or 1-(chloromethyl)-4-(2-propenyl)benzene; (ii)hydroarylation of norbornadiene in the presence of a palladium catalystand haloarene (e.g., 1-(bromomethyl)-4-iodobenzene to to yield NBPhCH₂BrXXIV-a); and (iii) by reduction of norbornene carboxaldehydes,carboxylic acids, carboxylic acid esters, and nitriles to norbornenehydroxyls which are are readily converted to chloro, bromo, or iodoalkyls, i.e., NB(endo-CH₃)(exo-CO₂H)NB(endo-CH₃)(exo-CO₂H)→NB(CH₃)(CH₂OH)→NB(CH₃)(CH₂Cl) orNBCN→NBCHO→NBCH₂OH→NBCH₂Cl.

While each formula XVIII-a, XX-a and XXV-a, provided above, are depictedwithout indication of any stereochemistry, it should be noted thatgenerally each of these monomers and other monomers produced for thepurpose of this disclosure, unless indicated otherwise, are obtained asdiastereomeric mixtures that retain their configuration when convertedinto repeating units. As previously noted and discussed, the exo- andendo-isomers of such diastereomeric mixtures can have slightly differentchemical and physical properties, it should be further understood thatsome embodiments in accordance with the present disclosure are made totake advantage of such differences by using monomers that are either amixture of isomers that is rich in the advantageous isomer or areessentially the pure advantageous isomer. The XXI-a and XXII-astructures exemplified are embodiments of this disclosure where themonomer employed possesses an exo-substituted functional group and assuch is anticipated as being more readily polymerized and converted tothe quaternary ammonium salt.

In some embodiments, the base stability of the quaternary amines can beimproved, for example in compound XI, by increasing the aliphatic chainlength of the alkyl substituent, NB(CH₂)n[NMe₃]Cl (n=1-6). Improvementsin base properties are, for example, low swelling in hot methanol, highion exchange capacity (IEC), good hydroxide ion conductivity, polymerstability, and mechanical strength.

Compounds XIX through XXIV have improved membrane stability underalkaline conditions compared to compound XVI because the incorporationof trimethylammonium groups in structures which do not possessβ-hydrogen atoms thus preventing degradation by Hofmann elimination.

In other embodiments, the polymers will be substituted with a singlealkyl trimethylammonium cation per polycyclic structure, but byappropriate selection of a functional norbornene additional quaternaryammonium moieties may be introduced to to improve ion conductivity. Themechanical strength of the films is adjusted via the incorporation ofone or more functional norbornene monomers, such as alkylNB (e.g.,decylNB, hexylNB, butylNB); methyl glycol ether NB (e.g.,NBCH₂(OCH₂CH₂)₂OMe NBCH₂(OCH₂CH₂)₂OMe and NBCH₂(OCH₂CH₂)₃OMe);NB-ether-NB (e.g., NBCH₂OCH₂NB, NBCH₂(OCH₂CH₂)₂OCH₂NB, andNBCH₂(OCH₂CH₂)₃OCH₂NB), NBCH₂(OCH₂CH₂)₃OCH₂NB), NB-alkylene-NB (e.g.,NB-NB, NB-Et-NB NB-Bu-NB, and NB-Hx-NB); NB-aryl-NB (e.g., NBC₆H₄NB andNBCH₂C₆H₄CH₂NB); and maleimide-alkyl-NB (e.g., NBMeDMMI, NBPrDMMI,NBBuDMMI, and NBHxDMMI), which may be crosslinked in either 100%reactive solids polymerization, or via acid or base catalyzed, thermal,and photochemical reactions of polynorbornene films.

In other embodiments in accordance with the present disclosure, the useof a difunctional amine, polycyclic amine or dendrimer polyamine, or acyclic diamine, such as DABCO (1,4-diazabicyclo(2,2,2)octane), can beemployed during film casting as a crosslinker unit to create ammoniumfunctions that are less sensitive to the Hoffman elimination reactionand the substitution by hydroxyl group, and it allows for the thermalcrosslinking via its second nitrogen. Quinuclidine has a structure thatis similar to that of DABCO which confers a good resistance with respectto Hoffman degradation and nucleophilic substitution by OH⁻ ion. Themethod to produce crosslinked films is exemplified as follows:

Other cross-linker moieties that can be employed during film castinginclude, among others, bis(dimethylamino) moieties such as:1,4-diazabicyclo[2.2.2]octane, 2-methyl-1,4-diazabicyclo[2.2.2]octane,N¹,N¹,N³,N³-tetramethyl-1,3-propanediamine,N¹,N¹,N³,N³-tetramethyl-1,3-propanediamine,N¹,N¹,N³-2-tetramethyl-1,3-propanediamine,N¹,N¹,N³,N³-2-pentamethyl-1,3-propanediamine,N¹,N¹,N³,N³-tetramethyl-1,3-butanediamine,N¹,N¹,N²,N²-tetramethyl-1,2-propanediamine,N¹,N¹,N³,N³,2,2-hexamethyl-1,3-propanediamine,N¹,N¹,N⁶,N⁶-tetramethyl-1,6-hexanediamine,N¹,N¹,N¹⁰,N¹⁰-tetramethyl-1,10-decanediamine,N¹,N¹,N¹²,N¹²-tetramethyl-1,12-dodecanediamine,N¹,N¹,N³,N³-tetramethyl-1,3-butanediamine,N³-[2-(dimethylamino)ethyl]-N¹,N¹-dimethyl-1,3-propanediamine,N¹-[2-(dimethylamino)ethyl]-N¹,N¹-(1-methylethyl)-1,3-propanediamine,N¹-[2-(dimethylamino)ethyl]-N²,N²-dimethyl-1,2-propanediamine,N¹,N¹,N⁴,N⁴-tetramethyl-1,4-benzenedimethanamine,4-[2-(dimethylamino)ethyl]-N,N-dimethylbenzenemethanamine,N¹,N¹,N³,N³-tetramethyl-1,3-benzenedimethanamine,N¹,N¹,N⁴,N⁴-tetramethyl-1,4-cyclohexanedimethanamine, andN¹,N¹,N⁴,N⁴-tetramethylbicyclo[2.2.2]octane-1,4-dimethanamine.

Aromatic cross-linker moieties include, but are not limited to,N³,N³,N⁶,N⁶-tetramethyl-3,6-Phenanthrenedimethanamine,N₉,N₉,N₁₀,N₁₀-tetramethyl-9,10-Anthracenedimethanamine,N₁,N₁,N₅,N₅-tetramethyl-1,5-Naphthalenedimethanamine,N²,N²,N⁶,N⁶-tetramethyl-2,6-Naphthalenedimethanamine,N¹,N¹,N⁸,N⁸-tetramethyl-1,8-Naphthalenedimethanamine,N²,N²,N⁶,N⁶-tetramethyl-1,8-Naphthalenedimethanamine,N¹,N¹,N⁴,N⁴-tetramethyl-1,4-Benzenedimethanamine,N¹,N¹,N³,N³-tetramethyl-1,3-Benzenedimethanamine,N¹,N¹,N²,N²-tetramethyl-1,2-Benzenedimethanamine,N⁴,N⁴,N⁴′,N⁴′-tetramethyl-[1,1′-Biphenyl]-4,4′-dimethanamine,N⁵,N⁵,N¹⁴,N¹⁴-tetramethyl-Tricyclo[9.3.1.14,8]hexadeca-1(15),4,6,8(16),11,13-hexaenene-5,14-dimethanamineand 9,10-dihydro-N²,N²,N⁷,N⁷-tetramethyl-2,7-Anthracenediamine,2,7-bis[(dimethylamino)methyl]-9,10-Anthracenedione,2,6-bis[(dimethylamino)methyl]-9,10 Anthracenedione,9,10-dihydro-N²,N²,N⁶,N⁶-tetramethyl-2,6-Anthracene dimethanamine,N³,N³,N⁶,N⁶-tetramethyl-9H-Fluorene-3,6-diamine,2,6-bis[(dimethylamino)methyl]-1,5-dihydroxy-9,10-Anthracenedione.

Still other cross-linker moieties can be employed during film castinginclude, among others, dibromo, chloro/bromo, tri-bromo, iodo and chloromoieties such as: 1,2-dibromopropane, 1,2-dibromoethane,1,2,3-tribromopropane, 1,3-dibromobutane, 1,3-dibromobutane,1,3-dibromo-2,2-dimethylpropane, 2,4-dibromopentane, 1,4-dibromobutane,1-bromo-3-(bromomethyl)octane, 2,5-dichloro-2,5-dimethylhexane,2-bromo-4-(2-bromoethyl)octane,1,5-dibromooctane,1-bromo-4-(bromomethyl)octane, 1-bromo-3-(2-bromoethyl)heptane,1-bromo-3-(2-bromoethyl)-4,4-dimethylpentane, 2,5-dibromohexane,1,4-dibromo-heptane, 2,4-dibromo-2-methylpentane, 1,10-dibromoundecane,1-bromo-3-(2-bromoethyl)-4,4-dimethylpentane,2-bromo-4-(2-bromoethyl)octane, 1,5-dibromo-3,3-dimethylpentane,1-bromo-4-(bromomethyl)octane, 1-bromo-3-(2-bromoethyl)heptane,1-bromo-3-(bromomethyl)octane, 1,10-dibromodecane, 1,11-dibromoundecane,1,10-dibromoundecane, 2,4-bis(bromomethyl)pentane, 1,12-dibromododecane,1,13-dibromotridecane, 1,5-dibromo-3-methylpentane, 1,8-dibromooctane,1,9-dibromononane, 1,5-dibromooctane, 1,2-dibromododecane,1,4-bis(bromomethyl)cyclohexane, 1,2,6-tribromohexane,1,2,5,6-tetrabromohexane, 1,4-bis(bromomethyl)bicyclo[2.2.2]octane,1,1-bis(bromomethyl)cyclohexane, 1,1-bis(bromomethyl)cyclooctane,1,1-bis(bromomethyl)-2-methylcyclohexane,trans-1,4-bis(1-bromo-1-methylethyl)cyclohexane,1,4-bis(1-bromo-1-methylethyl)cyclohexane,1,3,5-tris(bromomethyl)-1,3,5-trimethylcyclohexane,cis-1,5-bis(bromomethyl)cyclooctane,trans-1,2-Bis(bromomethyl)cyclohexane,trans-1,5-bis(bromomethyl)cyclooctane, 1,1-bis(bromomethyl)cycloheptane,1,4-bis(bromomethyl)benzene, 1-(bromomethyl)-4-(chloromethyl)benzene,1-(2-bromoethyl)-4-(bromomethyl)benzene, 1,3-diiodo-2,2-dimethylpropane,1,3-diiodo-2,2-bis(iodomethyl)propane, 1,3-diiodopropane,1-bromo-3-chloro-2-methylpropane, 1,3-dibromo-2-methylpropane,1,5-diiodo-3-methylpentane, 1,4-diiodobutane, 1,3-diiodopentane,1,5-diiodopentane, 1,5-diiodopentane, 1-chloro-3-iodopropane,1-bromo-3-iodopropane,1,3-dichloro-2,2-dimethylpropane,1,4-bis(chloromethyl)cyclohexane, 1,4-bis(iodomethyl)benzene,4-bis(2-iodoethyl)benzene; and 1,2-bis(iodomethyl)benzene.

Yet other cross-linker moieties include:N¹,N²-bis[2-(dimethylamino)ethyl]-N¹,N²-dimethyl-1,2-EthanediamineN¹,N¹-bis[2-(dimethylamino)ethyl]-N²,N²-dimethyl-1,2-EthanediamineN¹-[2-(diethylamino)ethyl]-N²,N²-diethyl-N¹-methyl-1,2-EthanediamineN¹-[2-(dimethylamino)ethyl]-N¹,N²,N²-trimethyl-1,2-EthanediamineN-[(dimethylamino)methylethylkN,N′,N′-trimethyl-1,2-PropanediamineN¹-[2-[[2-(dimethylamino)ethyl]methylamino]ethyl]-N¹,N³,N³-trimethyl-1,3-PropanediamineN¹,N³-bis[2-(dimethylamino)ethyl]-N¹,N³-dimethyl-1,3-Propanediamine, and3-[2-(dimethylamino)ethyl]-N¹,N¹,N⁵,N⁵,3-pentamethyl-1,5-Pentanediamine

To further illustrate such cross-linking moieties, the following arestructural representations of some of the of the above named moieties:

The following examples are provided to further illustrates aspects ofsome embodiments of the present disclosure. It should be understood thatsuch examples are in no way limiting to the scope of such embodimentsand are presented for illustrative purposes only.

MONOMER SYNTHESIS EXAMPLES Example M1 Synthesis ofEndo-5-Methyl-Exo-5-Carboxylic Acid-2-Norbornene

Freshly cracked cyclopentadiene (939 grams, 14.2 moles) and methacrylicacid (1203 grams, 14.2 moles) were added to an appropriately sizedcontainer containing a magnetic stirrer. The contents were stirred for24 hours and then left to stand without stirring for 60 hours, overwhich time a white powder was observed to precipitate from fromsolution. To encourage precipitation, the flask was cooled at 10° C. forseveral hours. The precipitate was collected by vacuum filtration andrinsed with cold pentane pentane (2 L, −10° C.) to remove any un-reactedstarting material and any NB(exo-Me)(endo-CO₂H) by product that may haveformed. The precipitated white powder (700 g) was recrystallized inhexanes (˜50 wt %) to give transparent crystals of ofNB(endo-Me)(exo-CO₂H) (621 g, 29%) upon cooling over 24 hours.

The monomer was characterized by ¹H NMR and ¹³C NMR. The numberingsystem shown in the following figure was used for the assignment of theNMR signals.

NMR (500 MHz, CDCl₃): δ (ppm)=6.25 (dd, 1H, J=5.59 & 2.96, H_(2&3)),6.12 (dd, 1H, J=5.59 & 3.17, H _(2&3)), 3.07 (s, 1H, H_(1&4)), 2.86 (s,1H, H_(1&4)), 2.45 (dd, 1H, J=12.02 & 3.96, H₇), 1.48 (m, 2H, H₆), 1.18(m, 3H, H₈), 0.89 (m, 1H, J=12.02, H_(7′)). ¹³C NMR (125.6 MHz, CDCl₃):δ (ppm)=186.03, 139.03, 133.82, 50.71, 49.77, 49.32 43.13, 37.64 and24.49.

Example M2 Synthesis of Endo-5-Methyl-Exo-5-Methyl Hydroxy-2-Norbornene

NB(endo-Me)(exo-CO₂H) (174.8 g, 1.15 mmol) and anhydrous toluene (1000mL) mL) were added to an appropriately sized container and kept undernitrogen. The container was equipped with a magnetic stirrer bar,thermometer, addition-funnel and condenser. A pre-mix of Vitride® (500g, 70 wt % in toluene, 1.73 mol) was added to the the addition funnel(short exposure to air is acceptable if <2 minutes). With the containersubmerged in an ice-water bath, the dilute Vitride® was added dropwiseover 3 over 3 hours while maintaining pot temperature between 5-20° C.After the addition was was complete, the contents were heated to 100° C.for 6 hours (until thin layer chromatography (TLC) indicated a completedreaction). The contents were allowed to to cool overnight. The solutionwas slowly added to a beaker containing vigorously stirring 5N HCl (1000mL). The temperature was maintained <20° C. with the aid of an anice-bath. The mixture was transferred to a separatory funnel onceturbidity decreased. The organic phase was then diluted with diethylether (1.0 L) and the aqueous aqueous phase was discarded. The organicswere washed with a solution of 1N HCl (3×300 mL), 15 wt % aqueouspotassium bicarbonate (3×300 mL) and water (500 mL). Following, theorganics were dried over MgSO₄, then filtered, and the solvent removedremoved under reduced pressure to yield NB(endo-Me)(exo-CH₂OH) (152 g,96%, in >>95% purity).

The monomer was characterized by ¹H NMR and ¹³C NMR. The numberingsystem shown in the following figure was used for the assignment of theNMR signals.

¹H NMR (300 MHz, CDCl₃): δ (ppm)=6.12 (m, 2H, H_(2&3)), 3.56 (m, 2H,H₉), 2.76 (bs, 1H, H_(1&4)), 2.55 (bs, 1H, H_(1&4)), 2.14 (m, 1H, H₁₀),1.55 (d, 1H, J=8.62, H₆), 1.44 (m, 1H, J=11.72 & 3.71, H₇), 1.35 (d, 1H,J=8.62, H₆), 0.91 (s, 3H, H₈), 0.77 (m, 1H, J=11.72 & 2.68, H_(7′)). ¹³CNMR (75 MHz, CDCl₃): δ (ppm)=136.75, 135.68, 72.26, 47.85, 47.61, 43.70,37.34, 22.87.

Example M3 Synthesis ofEndo-5-Methyl-Exo-5-Methoxy-Mesylate-2-Norbornene

NB(endo-Me)(exo-CH₂OH) (74.8 g, 540 mmol) was dissolved in 250 mldichloromethane in appropriately sized container. Methanesulfonylchloride (MSCI) (65.6 g, 0.54 mol) was added. The mixture was thencooled to −12.5° C. with a methanol-ice bath. Triethylamine (65.6 g, 650mmol) was added slowly dropwise while while maintaining the reactiontemperature below −1.0° C. Copious white solids precipitated. Theaddition was complete after 30 minutes. The reaction warmed to 14° C.for 40 minutes. GC analysis showed all starting material had beenconsumed. The The mixture was treated with 200 ml water and the phasesseparated. The organic phase phase was washed with 200 ml 1N HClfollowed by brine until the washing gave pH˜6. pH˜6. The organic portionwas dried over anhydrous magnesium sulphate, filtered, and and rotaryevaporated to give 100 g (90% yield) of NB(endo-Me)(exo-CH₂OMs) as apale orange liquid.

The monomer was characterized by ¹H NMR. The numbering system shown inthe following was used for the assignment of the NMR signals.

¹H NMR (400 MHz, CDCl₃): δ (ppm)=6.11 (m, 1H, H_(2&3)), 6.10 (m, 1H,H_(2&3)), 4.10 (s, 2H, H₉), 2.96 (s, 3H, H₁₀), 2.78 (s, 1H, H_(1&4)),2.57 (s, 1H, H_(1&4)), 1.48 (m, 2H), 1.39 (m, 1H), 0.91 (s, 3H, H_(s)),0.80 (m, 1H, H_(7′)).

Example M4 Synthesis of Endo-5-Methyl-Exo-5-Bromomethyl-2-Norbornene

NB(endo-Me)(exo-CH₂OMs) (10.3 g, 46.3 mmol), anhydrous lithium bromide(6.2 g, 69.4 mmol), and 100 ml 2-pentanone were mixed together at roomtemperature to to give a yellow solution. The mixture was refluxed fortwo hours and then allowed to stir at room temperature overnight. Waterwas added to dissolve the salts. Ethyl acetate acetate was added andmixed. The phases were separated and the aqueous phase was extractedwith 2×100 ml ethyl acetate. The organic portions were dried overanhydrous anhydrous sodium sulfate, filtered, and rotary evaporated togive a brown oil and solid. solid. The crude product was shown tocontain a ratio ofNB(endo-Me)(exo-CH₂OMs): NB(endo-Me)(exo-CH₂OMs):NB(endo-Me)(exo-CH₂Br)=1:3 respectively by ¹H NMR. The crude product waspurified via column chromatography on silica gel (35 g) and cyclohexane(250 mL) to give clear, colorless oil. R_(f) (cyclohexane)=0.80.Yield==65%.

The monomer was characterized by ¹H NMR and ¹³C NMR. The numberingsystem shown in the following figure was used for the assignment of theNMR signals.

¹H NMR (400 MHz, CDCl₃): δ (ppm)=6.15 (dd, 1H, J=5.60 & 2.80, H₃), 6.11(dd, 1H, J=5.60 & 3.20, H₂), 3.56 (s, 1H, H₈), 2.82 (s, 1H, H₄), 2.65(s, 1H, H₁), 1.65 (dd, 1H, J=11.98 & 3.75, H₇), 1.54 (d, 1H, J=8.91,H₆), 1.42 (d, 1H, J=8.91, H₆), 1.01 (s, 1H, H₉), 0.97 (dd, 1H, J=12.98 &2.72, H_(7′)). ¹³C NMR (101 MHz, CDCl₃): δ (ppm)=137.09 (C₂), 135.78(C₃), 50.24 (C₄), 48.29 (C₈), 47.96 (C₆), 43.68 (C₁), 40.16 (C₇), 27.15(C₅), 24.86 (C₉).

Example M5 Synthesis of Endo-/Exo-bromobutylnorbornene

Endo-/exo-norbornenebutyl mesylate: 5-(2-hydroxybutyl)norbornene (1000g, 6 mol), 2000 ml dichloromethane, and methanesulfonyl chloride (723.4g, 6.32 mol) were were added to an appropriately sized containerequipped with a thermoweli, nitrogen inlet, addition funnel andmechanical stirrer. An additional 500 mL dichloromethane was added torinse in the methanesulfonyl chloride (MsCl). The stirred mixture waschilled to −14.0° C. with a dry ice-isopropanol cooling bath.Triethylamine (733.6 g, 7.26 7.26 mol) was added rapidly dropwise over a2 hr and 20 minute period with the temperature ranging from −14° to −6°C. GC analysis showed no remaining NBBuOH. The resulting slurry wasallowed to warm during 3 hrs to room temperature. 1000 ml water was thenadded. The phases were separated and the aqueous phase extracted withwith 1000 ml dichloromethane. The combined dichloromethane extracts werewashed with 2 times 1 L IN HCl and then washed with 1000 ml brine, 1000ml saturated NaHCO₃, and 2000 ml brine. The dichloromethane solution wasdried over sodium sulfate, filtered, and rotary evaporated to give 1570g (quantitative yield) of red-brown red-brown liquid. The NMR wasconsistent with structure and showed 5.4 wt % dichloromethane remaining.The GC analysis indicated 96.6% mesylate purity. Furthermore, the GCanalysis was completed on a DB5 Column, 30 meters, 0.32 mm ID, ID, 0.25μm film, heat from 75° C. to 300° C. @15° C./min, and held for 2 min@300° C. (Injector temperature: 250° C., Detector temperature: 350° C.,Retention time: 11.216 minutes)

Endo-/exo-bromobutylnorbornene: Lithium bromide (LiBr) (782 g, 9.0 mol)and 12 L of 2-pentanone were added to an appropriately sized containerequipped with a thermowell, condenser with nitrogen adapter, andmechanical stirrer. The mixture was stirred yielding a yellow solution.Norbornene-butylmethanesulfonate (1570 g, ˜6.01 mol) was dissolved in 2L of 2-pentanone and added to the LiBr solution. An additionaladditional 4 L of 2-pentanone (total volume of 2-pentanone totaled 18 L)was added as rinse. The mixture was heated to reflux over a period of1.5 hrs to yield a white slurry. Upon reaching reflux (101° C.), the GCanalysis showed no starting material. The mixture was heated anadditional hour at 101° C. and then cooled to 17° C. Two litersdistilled water was added to clear the mixture. The mixture cloudedagain after a few minutes stirring, therefore, an additional 1 liter ofwater was added. The phases were separated. The reactor was rinsed with2×1000 ml ethyl acetate. The aqueous phase was then extracted with twotimes 1 L ethyl acetate washes. The organic portions were combined androtary evaporated at <30° C. to give 1579 g liquid and solids. The GCanalysis showed 96.9% NBBuBr. The residue was mixed with 1 Ldichloromethane and and 1 L water to dissolve all solids. The phaseswere separated. The organic portion was washed with 500 ml saturatedsodium bicarbonate and 500 ml brine to pH 7. The organic portion wasrotary evaporated to yield a 1419 g of a brown, clear oil. The NMR NMRanalysis indicated 2.3 wt % of 2-pentanone still remaining. Ten ml ofwater was added and the material rotary evaporated again. However, theNMR indicated no reduction in 2-pentanone. The product was then driedover sodium sulfate, rinsed with with dichloromethane and rotaryevaporated to give 1375 g (99.6% yield). GC indicated indicated 97.3%purity. The material was vacuum distilled through a 14″ Vigreux columnat 74.2-76.2° C. (0.22-0.53 Torr) to give 511.2 g with 98.5% purity,379.4 g (69.3-76.0° C. at 0.164-0.33 Torr) with 97.5% purity, and 309 g(68-77° C. at 0.245-0.72 Torr) with 95-96% purity. The GC analysiscompleted on a DB5 Column, 30 meters, 0.32 mm ID, 0.25 μm film, heatfrom 75° C. to 300° C. at 15° C./min, hold for 2 min @ 300° C., Injectortemperature: 250° C., Detector temperature: 350° C., Retention time:8.584 and 8.616 minutes.

Example M6 Synthesis of Endo-/Exo-bromoethylnorbornene

Endo-/exo-norborneneethylmesylate: 5-(2-hydroxyethyl)norbornene (NBEtOH)(1000 g, 7.235 mol), 2000 ml dichloromethane, and methanesulfonylchloride (871.6 g, 7.609 mol) were added to an appropriately sizedcontainer equipped with a thermowell, nitrogen inlet, addition funneland mechanical stirrer. An extra 1500 mL dichloromethane was added torinse in the methanesulfonyl chloride. The stirred mixture was chilledto −14° C. with a dry ice-isopropanol cooling bath. Triethylamine (883g, 8.74 mol) was added rapidly dropwise over 70 minutes as thetemperature ranged from −14° C. to −4° C. The reaction mixture becamevery thick, therefore, to improve mixing an additional 550 ml ofdichloromethane was added. The GC analysis showed <0.3% NBEtOH. Theresulting slurry was allowed to warm to room temperature while stirringovernight. The GC analysis showed 95.5% mesylate, 1.0% NBEtCI, and <0.2%NBEtOH. 1000 ml of water was added to clear the mixture. A second 500 mlportion of water was added, which clouded the mixture. The phases wereseparated and the aqueous phase extracted with two times 500 ml ofdichloromethane. The combined dichloromethane extracts were washed with1000 ml 1 N HCl, 1000 ml saturated NaHCO₃, and 2 times 1000 ml of brine.The dichloromethane solution was dried over sodium sulfate, filtered,and rotary evaporated to give approximately 1600 g (quantitative yield)of brown liquid. The NMR was consistent with structure and showed 1.4 wt% dichloromethane remaining. The GC analysis indicated 94.6% mesylatepurity. The GC analysis was completed on a DB5 Column, 30 meters, 0.32mm ID, 0.25 μm film, heat from 75° C. to 300° C. @15° C./min, hold for 2min @300° C., Injector temperature: 275° C., Detector temperature: 350°C., Retention time: 7.856 minutes.

Endo-/exo-bromoethylnorbornene: Lithium bromide (943 g, 10.83 mol) and11.5 L 11.5 L of 2-pentanone were added to an appropriately sizedcontainer equipped with a thermowell, a condenser with nitrogen adapter,and a mechanical stirrer. The mixture was stirred to give a yellowsolution. Norbornene-ethylmethanesulfonate (1604 g, ˜7.235 mol) wasdissolved in 3.5 L of 2-pentanone and added to the LiBr solution. Anadditional 1.5 L of 2-pentanone (total volume of 2-pentanone =16.5 L)was added as rinse. The mixture was heated to reflux over a period of1.75 hours to give a slurry. Upon reaching reflux (99° C.), the GCanalysis showed no starting material. The mixture mixture was heated anadditional 30 minutes at 99-102° C. The mixture was then cooled cooledto 25° C. Two liters of distilled water was added to clear the mixtureand followed with an additional 1 liter of water which clouded themixture. The phases were were separated. The reactor was rinsed with twotimes 1000 ml portions of ethyl acetate. The aqueous phase was thenextracted with two times 1000 ml ethyl acetate washes. The organicportions were combined and rotary evaporated at <30° C. When a asubstantial amount of 2-pentanone was removed, 200 ml water was addedand the mixture rotary evaporated at 45-50° C. This was done until noadditional condensate was was recovered. This yielded 1630 g brownliquid. The residue was mixed with 1 L of dichloromethane and 1 L ofwater. The phases were separated. The organic portion was was washedwith 500 ml saturated sodium bicarbonate and 1000 ml brine to pH 7. Theorganic portion was dried over sodium sulfate, filtered, and rotaryevaporated to give 1416 g red-brown oil (96.8% yield). The NMR analysisindicated traces of 2-pentanone 2-pentanone and some dichloromethanestill remaining. GC indicated 96.7% purity.

The material was initially vacuum-distilled through a 14″ Vigreux columnwhere the product retained a yellow coloration. An additionaldistillation through a 10″ glass helix-packed produced slightlyyellow-colored material. The distillates with 96-97.6% purity, totaling605 g, were dissolved in 1000 ml of dichloromethane, boiled with DarcoG-60 activated carbon, filtered, washed with two times 100 ml of 10%aqueous sodium bisulfate, 200 ml brine, a mixture of 100 ml saturatedsodium bicarbonate and 100 ml brine, and two times 200 ml of brine.After drying over sodium sulfate, this was rotary evaporated to a nearlycolorless material. Vacuum distillation through a 10″ glass helix-packedcolumn at 48-53° C. (0.69-0.95 Torr) gave 236 g colorless liquid with98.3% purity and containing 0.3% NBEtCl, 0.3% NBEtOH, and 0.9%dihydroNBEtBr. Also obtained was 117 g colorless liquid with 97.4-97.8%purity and 168 g colorless liquid with 96.6-96.8% purity.

The distillates with >98% purity, totaling 576 g, were dissolved in 1000ml dichloromethane, washed with 2×100 ml 10% aqueous sodium bisulfite,200 ml brine, a mixture of 100 ml saturated sodium bicarbonate and 100ml brine, and 2×200 ml brine. After drying over sodium sulfate, this wasrotary evaporated to still give a yellow liquid. Vacuum distillationthrough a 10″ glass helix-packed column at 48-54° C. (0.76-1.30 Torr)yielded 245 g colorless liquid with 98.2-98.5% purity and containing0.3-0.6% NBEtCl, 0.4-0.6% NBEtdH, and 0.6-0.8% dihydroNBEtBr. Alsocollected were 35.7 g colorless liquid with 97.8% purity. The last twodistillation cuts, totaling 266 g with >98% purity, were still slightlyyellow and were redistilled through the 10″ glass helix-packed column at43-50° C. (0.46-1.00 Torr) to give 251 g of colorless liquid with98.2-98.8% purity and containing <0.2% NBEtC1, <0.3% NBEtOH, and0.8-1.5% dihydroNBEtBr. The overall yield was 733 g of >98% purity(46.8% yield), 153 g with 97.4-97.8% purity (9.8% yield), and 168 g with96.6-96.8% purity (10.7% yield). GC analysis completed on a DB5 Column,30 meters, 0.32 mm ID, 0.25 μm film, Heat from 75° C. to 300° C. at 15°C./min, hold for 2 min @ 300° C., Injector temperature: 250° C.,Detector temperature: 350° C., Retention time: 4.305 and 4.332 minutes.

Example M7 Exo-bromomethylphenylnorbornene

Exo-hydroxymethylphenylnorbornene: An appropriate sized container wasequipped with a thermowell, addition funnel, condenser with nitrogeninlet and mechanical stirrer. The RBF was charged with Pd(PPh₃)₂Cl₂(29.2 g, 0.0416 mol) and (4-bromophenyl)methanol (194.6 g, 1.04 mol) in1 L of DMF (drysolv) under nitrogen blanket to give a light yellowturbid solution and stirred at room temperature for 5 minutes. Theaddition funnel was charged with 383.4 g of norbornadiene (4.16 mol),added as neat over 5 minutes and followed by 435.2 mL of triethylamine(3.12 mol). Then the addition funnel was charged with formic acid (98.11mL, 2.6 mol) and added to to the reaction mixture slowly at roomtemperature over 30 minutes and slight exotherm exotherm was observed(14° C. to 37° C.). The reaction mixture was heated to 70° C. and a alight orange solution resulted. At 70° C., an exotherm was observed andreaction temperature briefly reached 90° C. after which the temperaturewas maintained at 80° C. for 4 h. The reaction was monitored by gaschromatography (GC) (aliquot quenched with water water and extractedwith MTBE). The reaction was complete after 4 h stirring at 80° C. Thereaction was allowed to cool to room temperature and quenched with 2 Lwater and and diluted with 3 L methyl t-butyl ether. The phases wereseparated and the aqueous phase extracted with (2×1 L) methyl t-butylether. The combined organic layers were washed with (2×1 L) 10%hydrochloric acid, (2×500 mL) 5% lithium chloride aqueous aqueoussolution, (2×1 L) brine and dried over sodium sulfate, filtered, androtary evaporated under reduced pressure to give 391.9 g crude productas a light orange viscous oil. The 391.9 g crude product was adsorbedonto 400 g of silica and chromatographed over 3kg of silica gel elutingwith heptane (16 L), 5% ethyl acetate in in heptane (20 L), 7% ethylacetate in heptane (12 L), 10% ethyl acetate in heptane (18 L), (18 L),15% ethyl acetate in heptane (20 L) and 20% ethyl acetate in heptane (20L). The The concentrated purified fractions yielded 99 g of product aslight yellow viscous oil with 98.4% purity by GC and another fraction 73g of product with 88.2% purity by GC. GC. Proton nuclear magneticresonance spectroscopy (¹HNMR) and carbon-13 nuclear nuclear magneticresonance spectroscopy (¹³CNMR) were consistent with the desiredstructure. The combined yield for this reaction was 82.1% with >88.2%purity.

Exo-bromomethylphenyl norbornene: An appropriate sized container wasequipped with a thermowell, stopper, condenser with nitrogen inlet andmechanical stirrer. The RBF was charged withexo-hydroxymethylphenylnorboronene (99 g, 0.49 mol) in 1 L oftetrahydrofuran (anhydrous) under nitrogen blanket to give a lightyellow yellow solution and stirred at room temperature for 5 minutes.Then N-bromosuccinimide (105 g, 0.59 mol) and triphenylphosphine (154.8g, 0.59 mol) was was added as solid to the reaction in two portions at20° C. over lh (slight exotherm was was observed duringN-bromosuccinimide/triphenylphosphine addition). A light brown brownsolution resulted and the reaction was monitored by GC (aliquot quenchedwith water and extracted with methyl t-butyl ether). The reaction wascomplete after lh stirring at room temperature and the reaction mixturewas poured into 7 L pentane and the triphenylphosphine oxide byproductprecipitated as an off white crystalline solid. This solid was filteredthrough a pad of magnesium sulfate and the filtrate was concentrated togive 148 g crude product as light brown liquid. The 148 g crude productproduct was again diluted with 2 L pentane to remove the residualtriphenylphosphine oxide byproduct. The white turbid solution wasfiltered through a pad of magnesium sulfate and the filtrate wasconcentrated under reduced pressure to give 125.1 g of crude crudeproduct as a brown liquid. The 125.1 g crude product was transferred toa 500 mL mL RBF and purified via Kugelrohr distillation at 125-135° C.oven temperature under vacuum 0.112-0.14 Torr to give 90.9 g of productwith 98.2% purity by GC as a clear liquid. After keeping at roomtemperature the clear liquid turned dark brown, so the 90.9 g crudeproduct was adsorbed onto 100 g of silica and chromatographed over 400 gof silica gel eluting with pentane (4 L), 2% ethyl acetate in pentane (4L), 3% ethyl acetate in pentane (2 L) and 4% ethyl acetate in pentane (2L). The concentrated purified purified fractions yielded 87 g (66.9%) ofproduct as clear viscous oil with 98.8% purity purity by GC. ¹HNMR and¹³CNMR were consistent with the desired structure.

Example M8 Synthesis of2-(bicyclo[2.2.1]hept-5-en-2-yl)-N,N,N-trimethylethanaminium bromide

An appropriately sized container was charged under nitrogen withtetrahydrofuran (180 g, 202 mL), 2-bromoethyl norbornene (20.11 g, 100mmol) and a stock solution of trimethylamine (45% aqueous 65.7 g 79.1ml). The contents were stirred for 48 hours, at which time the solventswere removed under reduced pressure. A portion of drum grade toluene(200 ml, 173 g) was added. The solvents were then removed once againunder reduced pressure with the toluene being useful to promote theazeotropic removal of water. The azeotropic removal of water wasrepeated with toluene (200 ml 173 g) and subsequently with heptane (200ml, 136 g). The resulting powder was dried under vacuum for 18 hours.

The monomer was characterized by ¹H NMR. The numbering system shown inthe following figure was used for the assignment of the NMR signals.

¹NMR (500 MHz, CDCl₃): δ (ppm)=6.20 (dd, 1H, H_(2&3)), 6.03 (dd, 1H,H_(2&3)), 3.55-3.75 (2H, H₉), 3.4-3.55 (m, 9H, H₁₀) 2.84 (s, 1H,H_(1&4)), 2.63 (s, H_(1&4)), 2.05 (1H, H₇), 1.48 (2H, H₅), 1.38 (m, 1H,H₆), 1.21 (m, 2H, H₈), 0.59 (dd, 1H, J=12.02, H₇).

Example M9 Synthesis of 1,1′-(1,4-phenylene)bis(N,N-dimethylmethanamine)

An appropriate sized container was equipped with a thermowell, condenserwith a nitrogen inlet, addition funnel and mechanical stirrer. The RBFwas charged with formic acid (297.3 g, 244 mL, 6.46 mol) and cooled to10° C. 1,4-Bis (aminomethyl)benzene (88 g, 0.65 mol) was added portionwise to control the exotherm and gave a clear solution. The additionfunnel was charged with 37wt % aqueous formaldehyde (116.4 g, 315 mL,3.88 mol) and added slowly over 15 minutes. The mixture was heatedcarefully (to avoid excessive foaming) to reflux over 30 minutes. Avigorous evolution of carbon dioxide was observed at 86° C., at whichtime the heating mantle was removed until the gas evolution notablysubsided; heat was reapplied and the reaction mixture was stirred at˜90° C. for 18 h. After 18 h, aliquot GC indicated that the reaction wascompleted (95.2% product with 4.13% intermediate(1,1′-(1,4-phenylene)bis(N-methylmethanamine))). The reaction mixturewas cooled to room temperature and added 5% excess reagents(formaldehyde/formic acid) and heated to reflux for another 24 h.Aliquot GC indicated no significant improvement in product purity so thereaction mixture cooled to room temperature and acidified with 500 mL 4Nhydrochloric acid and the clear solution was evaporated to dryness underreduced pressure at 90° C. bath temperature to give 121 g of crudeproduct as a white solid.

The white solid was dissolved in 200 mL water and basified with 250 mL20% aqueous sodium hydroxide solution and extracted with 600 mL toluene.The phases were separated and the aqueous layer was extracted with(2×200 mL) toluene. The combined organics were washed with 500 mL brine,dried over sodium sulfate and filtered through a pad of magnesiumsulfate. The filtrate was concentrated on the rotary rotary evaporatorat 60° C. bath temperature to give 85.8 g (69.1% crude yield) product asas clear liquid with 96.1% purity and 3.5% intermediate(1,1′-(1,4-phenylene)bis(N-methylmethanamine)). The crude product wasfurther purified by reacting the intermediate(1,1′-(1,4-phenylene)bis(N-methyimethanamine))(1,1′-(1,4-phenylene)bis(N-methylmethanamine)) with excess Na—SiO₂ andfiltering through a pad of magnesium sulfate. The filtrate was dilutedwith toluene/methylene chloride and washed with water/brine,concentrated, and the crude material was further further purified viaKugelrohr distillation at 80-95° C. oven temperature under vacuum0.45-0.55 Torr to give 71.8 g (57.8% yield) of product with >99.3%purity by GC as a clear liquid. ¹HNMR, ¹³CNMR and MS were consistentwith the desired structure.

A. Synthesis of Polymers Examples P1a-1b ROMP Mass Polymerization ofHexNB/NBBuBr/NBBuNB

For the amounts of the various materials, see Table 1 below.5-Hexylbicyclo[2.2.1]hept-2-ene (HexNB),5-(4-bromobutyl)bicyclo[2.2.1]hept-2-ene (NBBuBr) and1,4-di(bicyclo[2.2.1]hept-5-en-2-yl)butane (NBBuNB) were weighed andtransferred into an appropriately sized container. A catalyst solutionof [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-[2-[[(2-methylphenyl)imino]methyl]-phenolyl]chloro-(3-phenyl-indenylidene)ruthenium(II)in toluene was prepared in a separate vial. The catalyst solution wasadded to the monomer mixture. The polymerization mixture was poured intoa petri dish. The mixture was heated at 80° C. for minutes and 130° C.for 30 minutes to complete.

Examples P2a-2b 2,3 Vinyl Addition Mass Polymerization

5-Hexylbicyclo[2.2.1]hept-2-ene (HexNB),5-(4-bromobutyl)bicyclo[2.2.1]hept-2-ene (NBBuBr) and1,4-di(bicyclo[2.2.1]hept-5-en-2-yl)butane (NBBuNB) were weighed andtransferred into an appropriately sized container. A catalyst solutionof (acetato-O)(acetonitrile)bis[tris(1-methylethyl)phosphine]palladiumtetrakis(2,3,4,5,6-pentafluorophenyl)borate in toluene was prepared in aseparate vial. The catalyst solution was added to the monomer mixture.The polymerization mixture was poured into a petri dish. The mixture washeated at 80° C. for minutes and 130° C. for 30 minutes to complete.

TABLE 1 Polymerization* Ex # Ru Catalyst Pd Catalyst HexNB NBBuBr NBBuNBToluene P1a 0.015 0.40 1.05 0.56 2.00 P1b 0.015 0.78 0.73 0.51 2.00 P2a0.02 0.40 1.04 0.55 2.51 P2b 0.02 0.76 0.73 0.51 2.52 *All values are ingrams

Example(s) P3a-3l Synthesis of NB-alkyl/NB-alkylbromide Polymers ExampleP3a

Synthesis of 53% NB-EtBr/47% Hexyl NB Polymer. While the following isthe specific procedure used for the synthesis of the named polymer, oneof ordinary skill in the art will appreciate that such procedure canalso be viewed as a general procedure for solution polymerization toproduce the polymers listed in Table 2, or any otherNB-alkyl/NB-alkylbromide type polymer, where the substitution ofappropriate ratios of selected monomers, and appropriate amounts ofcatalyst and solvents are made.

An appropriately sized container was charged under nitrogen with drumgrade toluene (510 g, 589.6 mL), 5-hexylbicyclo[2.2.1]hept-2-ene (Hexylnorbornene, 70.01 g, 392.6 mmol),5-(4-bromobutyl)bicyclo[2.2.1]hept-2-ene (Bromobutyl norbornene, 29.99 g130.9 mmol) and ethyl acetate (24.95 g, 27.66 ml). The mixture was heldat 40° C. in a constant temperature oil bath, while being sparged withnitrogen for 15 minutes. A solution of Ni(toluene)(C₆F₅)₂ (3.17 g 6.54mmol) in ethyl acetate (31.7 g 35.2 ml) was added in one portion to thevigorously stirred reaction mixture. The reaction was stirred vigorouslyand held at 40° C. for four hours, at which time the reaction wasquenched by the addition of deionized water (10 ml). Residual nickelmetal was removed by treatment of the reaction mixture with hydrogenperoxide (35% aqueous solution 10 g) and glacial acetic acid (97+%, 10g) and stirring was continued for two hours while maintaining thetemperature at 40° C.

The reaction mixture was transferred to a 1 L separatory funnel. Thereaction solution was washed with deionized water (5×250 ml) utilizingtetrahydrofuran (90.2 g 100 ml) to break the emulsion formed during thewashing process. The organic layer was decanted into a 2 L roundbottomed flask and the solvents were removed under reduced pressure. Theresultant mixture was a thick honey-like consistency. This thick thicksolution was diluted with tetrahydrofuran (180.4 g 200 ml) and theresultant solution was added drop wise into methanol (1582 g 2000 ml) toprecipitate the solid polymer. The solid polymer was collected byfiltration of the resulting slurry. The filter-cake was washed with aportion of methanol (79.1 g 100 ml) and allowed to dry on on the filterfor approximately one hour. The crudely dried polymer was transferred toa a crystallization dish, covered with a dust free paper, and dried for18 hours in a vacuum vacuum oven set to 50° C. at a pressure of 25 torr.Overall yield was 99 g (99%) of dried solid. The polymer molecularweight by GPC was Mn=27,501 a.m.u.; Mw=107,013 a.m.u.; PDI=3.89. Thepolymer composition as measured by ¹H NMR was 53 mole % % norborneneethyl bromide and 47 mole % hexyl norbornene.

TABLE 2 Feed Ratio Yield Ex# AlkylNB:AlkylbromideNB % Mw PDI NMRComposition P3a 1 hexyl:1 ethyl bromide 97 102,000 3.65 53% NB-EtBr 47%hexyl NB P3b ethyl bromide 95 65,300 3.30 Homopolymer homopolymer P3c 1hexyl:1 Butyl bromide 99 114,600 3.54 56% NB-BuBr 44% Hexyl NB P3d Butylbromide 99 81,100 2.90 Homopolymer homopolymer P3e 1 hexyl:1 Butylbromide 99 86,900 3.50 58% NB-BuBr 44% Hexyl NB P3f 3 hexyl:1ButylBromide 99 107,000 3.90 30% NB-BuBr 70% hexyl NB P3g 3 Decyl:1 Butylbromide 99 99,000 2.85 28% NB-BuBr 72% Decyl NB P3h 3 Decyl:1 ethylbromide 99 94,800 2.80 34% NB-EtBr 66% Decyl NB P3i 1 Hexyl:1 ethylbromide 99 151,800 4.70 52% NB EtBr 48% Hexyl NB P3j 3 Hexyl:2 75237,000 2.35 32% NB(endo-Me)(exo-CH₂Br) (endo-Me)(exo-CH₂Br) 68% HexylNB P3k 3 Hexyl:2 61 143,800 1.73 28% NB(endo-Me)(exo-CH₂Cl)(endo-Me)(exo-CH₂Cl) 72% Hexyl NB P3l 1 Hexyl:1PhCH₂Br 50 587,400 4.0745% NBPhCH₂Br 55% Hexyl NB

Example P4 Cross-Linked ROMP Polymerization

Exo-bromomethylphenylnorbornene (1.20 grams, 4.56 mmol) and hexylnorbornene (1.09 grams, 6.13 mmol) were weighed into a vial and toluene(13.0 grams) grams) was added. In a separate vial1,1′-(1,4-phenylene)bis(N,N-dimethylmethanamine) (0.09 gram, 0.48 mmol)was weighed and toluene (2.0 grams) was added. In another vialdimethybenzylamine (0.49 (0.49 gram, 3.63 mmol) was weighed and toluene(5.0 grams) was added. In the last vial, vial,1,3-Dimesitylimidazolidin-2-ylidene)(tricyclohexylphosphine)benzylideneruthenium dichloride (39.5 mg, 0.046 mmol) was weighed and toluene (3.0grams) was was added. All these solutions were mixed together and themixed solution was cast in a a petri dish without delay. After 20 hoursof slow evaporation of the solvent at room temperature, thepolymerization/cross liking reaction was heated in a inert oven at 85°C. ° C. for 75 minutes followed by at 130° C. to complete the reaction.

Formation of Films Film Example F1 Procedure for Casting Film andAmine/Hydroxide Treatment of the Film

Step 1: Preparation of Polymer Solution

The copolymer prepared example P3a (copolymer of HexNB/NBEtBr) of 20grams was dissolved in tetrahydrofuran (24 grams, 45 wt %). The polymersolution was filtered through a 2.7 micron glass fiber filter.

Step 2: Preparation of Film

The filtered polymer solution was cast on a glass plate with 20 mil gapusing a

Gardco adjustable film applicator. The cast film was air dried at roomtemperature. The edges of film were lifted by a razor and the film wasimmersed to deionized water to lift off completely from the glass plate.The resulting film was wiped and air dried.

Step 3: Quarternarization of Film

A sample film was placed between PTFE flanges. The sample film wassubmerged in trimethylamine 50 wt % aqueous solution for 47 hours. Theamine treated film was air dried for 12 hours. The film was then vacuumdried at least for 8 hours.

Step 4: Anion Exchange of Quarternarized Film

The sample film was submerged in 1N NaOH aqueous solution for 20-30minutes. The film was rinsed with deionized water and air dried.

Film Example F2 Procedure for Casting Film and Amine/Hydroxide Treatmentof the Film

Step 1: Preparation of Polymer Solution

The copolymer prepared example P3e (copolymer of HexNB/NBBuBr) of 38grams was dissolved in toluene (56 grams, 40 wt %). The polymer solutionwas filtered through a 1.0 micron PTFE filter.

Step 2: Preparation of Film

The filtered polymer solution was cast on a glass plate with 10 mil gapusing a Gardco adjustable film applicator. The cast film was air driedat room temperature until no tack. The film was then heated in an inertoven at 60° C. for 1 hour, 100° C. for 1 hour, 130° C. for 16 hours and150° C. for 1 hour. The edges of film were lifted by a razor and thefilm was immersed to deionized water to lift off completely from theglass plate. The resulting film was wiped and air dried.

Step 3: Quarternarization of Film

A sample film was placed between PTFE flanges. The sample film wassubmerged in trimethylamine 45 wt % aqueous solution for 24 hours. Theamine treated film was air dried for 12 hours. The film was then vacuumdried at least for 8 hours.

Step 4: Anion Exchange of Quarternarized Film

The sample film was submerged in IN NaOH aqueous solution for 20-30minutes. The film was rinsed with deionized water and air dried.

Film Example F3 Procedure for Cross Linked Casting Film andAmine/Hydroxide Treatment of the Film

Step 1: Preparation of Polymer Solution

The copolymer prepared example P3e (copolymer of HexNB/NBBuBr) of 38grams was dissolved in toluene (56 grams, 40 wt %). The polymer solutionwas filtered through a 1.0 micron PTFE filter. This polymer solution of12 grams was added 1.55 grams of1,1′-(1,4-phenylene)bis(N,N-dimethylmethanamine).

Step 2: Preparation of Film

The polymer solution was cast on a glass plate with 10 mil gap using aGardco adjustable film applicator. The cast film was air dried at roomtemperature until no tack. The film was then heated in an inert oven at60° C. for 1 hour, 100° C. for 1 hour, 130° C. for 16 hours and 150° C.for 1 hour. The edges of film were lifted by a razor and the film wasimmersed to deionized water to lift off completely from the glass plate.The resulting film was wiped and air dried.

Step 3: Quarternarization of Film

A sample film was placed between PTFE flanges. The sample film wassubmerged in trimethylamine 45 wt % aqueous solution for 24 hours. Theamine treated film was air dried for 12 hours. The film was then vacuumdried at least for 8 hours.

Step 4: Anion Exchange of Quarternarized Film

The sample film was submerged in 1N NaOH aqueous solution for 20-30minutes. The film was rinsed with deionized water and air dried.

Film Example F4 Procedure for Cross Linked Casting Film andAmine/Hydroxide Treatment of the Film

Step 1: Preparation of Polymer Solution

The copolymer prepared example P31 (copolymer of HexNB/NBPhCH₂Br) of 5.6grams was dissolved in toluene (32 grams, 15 wt %). The polymer solutionwas filtered through a 1.0 micron PTFE filter. This polymer solution of6.3 grams was added 0.17 gram ofN¹,N¹,N³,N³,2,2-hexamethylpropane-1,3-diamine.

Step 2: Preparation of Film

The polymer solution was cast on a glass plate with 20 mil gap using aGardco adjustable film applicator. The cast film was air dried at roomtemperature until no tack. The film was then heated in an inert oven at60° C. for 1 hour, 100° C. for 1 hour, 130° C. for 16 hours and 150° C.for 1 hour. The edges of film were lifted by a razor and the film wasimmersed to deionized water to lift off completely from the glass plate.The resulting film was wiped and air dried. The cross linked film wasnot soluble in toluene.

Step 3: Quarternarization of Film

A sample film was placed between PTFE flanges. The sample film wassubmerged in trimethylamine 45 wt % aqueous solution for 64 hours. Theamine treated film was air dried for 12 hours. The film was then vacuumdried at least for 8 hours.

Step 4: Anion Exchange of Quarternarized Film

The sample film was submerged in 1N NaOH aqueous solution for 20-30minutes. The film was rinsed with deionized water and air dried.

Film Example F5 Control—No Added Amine

A 25 g sample of a copolymer of5-(2-bromoethyl)-bicyclo[2.2.1]hept-2-ene (norbornenyl ethyl bromide, 48mol %) and 5-hexylbicyclo[2.2.1]hept-2-ene (hexyl norbornene, 48 mol %)was weighed into a 500 mL amber glass bottle and 75 g of chloroform(Fisher, HPLC Grade) was added. The bottle was sealed and placed on aWheaton laboratory roller at ambient temperature. The bottle was rolledat 50 rpm for 18 hours to produce a homogeneous, viscous solution. Thepolymer solution was filtered through a 0.5 micron Teflon filter using a35 psig nitrogen back pressure and filtrate was collected in a lowparticle, 250 mL amber bottle. A 10 g aliquot of the polymer solutionwas poured into a 60 mm Pyrex Petri dish and covered with a glass lid toprevent rapid solvent evaporation. The Petri dish was placed in a fumehood and allowed to stand at ambient temperature for 18 hours. Thesurface of the resulting film was not tacky when touched. The Petri dishwas transferred to a vacuum oven and dried under vacuum (23 inches Hg)at 40° C. for a further 18 hours. The resulting film was removed fromthe Petri dish by cutting the edge bead with a scalpel and immersing thefilm in 25 mL of deionized water. The film was then allowed to dry underambient conditions. The resulting film weighed 1.30 g and was measuredto be 97 microns thick.

Film Example F6 With Added N,N,N′,N′-tetramethyl-1,6-hexanediamine

A 13.08 g aliquot of the polymer solution prepared in Example 1 wastransferred into a 50 mL amber bottle.N,N,N′,N′-tetramethyl-1,6-hexanediamine (0.775 g, 9.0 mmol) was added tothe bottle containing the polymer solution and the bottle was sealed.The polymer solution was mixed by rolling at ambient temperature for 18hours hours on a Wheaton laboratory roller at 50 rpm. A 5.71 g aliquotof the resulting viscous viscous solution was poured into a 60 mm Petridish and covered with a glass lid to prevent rapid solvent evaporation.The Petri dish was placed in a fume hood and allowed allowed to stand atambient temperature for 18 hours. The surface of the resulting film wasnot tacky when touched. The Petri dish was transferred to a vacuum ovenand dried dried under vacuum (23 inches Hg) at 40° C. for a further 18hours. The resulting film was removed from the Petri dish by cutting theedge bead with a scalpel and immersing immersing the film in 25 mL ofdeionized water. The film was then allowed to dry under under ambientconditions. The resulting film weighed 1.38 g and was measured to be 102μm thick.

Film Example F7 Amine Treatment of P4 ROMP Cross Liked Film

ROMP film from the example P4 was submerged in trimethylamine 45 wt %solution for 24 hours. The amine treated film was rinsed with deionizedwater and the film was then vacuum dried at least for 8 hours.

B. Ionic Conductivity of the Film

Conductivity measurements are done in a four-point probe configurationusing

BekkTech conductivity clamp BT 110. The sample dimension is at least 2.0cm in length and at most 1.2 cm in width. A sinusoidal voltage (10 mV)is applied to the outer two electrodes and the impedance across theinner two electrodes is measured using HP 4284A precision LCR meter.Thus, R=V/I at the inner electrodes. In the configuration, the contactresistance at the inner electrodes is negligible since the currentflowing through them is nearly zero. The frequency of the sinusoidalvoltage is varied and (typically 20 Hz to 1 MHz). The value of impedanceis read at around the frequency where the phase angle is zero or nearlyzero. This impedance Z is used to calculate the conductivity of films.The conductivity a is defined as follows:

σ=L/(Z*W*T)

(W is sample width, T is sample thickness, L is the distance of twoelectrodes)

A 0.05 to 0.1 gram sample of an AAEM membrane in hydroxide form wasimmersed in a 10 mL of 0.01 M HCl standard for 24 hours. The solutionswere then titrated with a standardized NaOH solution. Control sampleshaving no membrane added were also titrated with NaOH. The differencebetween the volume required to titrate the sample and the control wasused to calculate the amount of hydroxide ions in the membranes.

The bromide form membrane was soaked in 1N NaOH solution for 20-30minutes minutes for conversion to the hydroxide form membrane. Thehydroxide form membrane was rinsed in deionized water and wiped off toremove water from the surface. The weight of this membrane was recorded.The membrane was dried under vacuum for 24 hours at room temperature.The difference of weights was used for water water uptake.

In the Tables 3 and 4 below, where presented, the values for TheoreticalIon Exchange Capacity (IEC) have the dimension milliequivalents per gram(meq/g), the values for Water Uptake are in wt %, the values for Modulusand Strength are in MPa, the values for Elongation are in % and thevalues for Conductivity (COND) are in milliSiemens per centimeter(mS/cm). The mechanical properties of the wet hydroxide form AAEMsamples were measured using Instron model 5564 (Instron Corporation,Norwood, Mass.) in accordance with the ASTM D822-D plastics standard.

TABLE 3 Ion Sam- Polymer IEC Conduc- ple Polymer Compo- IEC Water Meas-tivity ID Type sition NMR Uptake ured 30° C. 60° C. Fl AP 47.5/52. 52.76 — — 49.5 76.7 HexNB/ NBEtBr F2 AP 55/45 2.24 150 1.16 29.5 49.1HexNB/ NBBuBr F3 AP 55/45 2.24 34 1.09 22.7 42.5 HexNB/ NBBuBr F4 AP 55/45 2.08 76 1.38 42.7 70.6 HexNB/ NBPhCH₂Br P4 ROMP 55/45 2.08 — — 1.234.59 HexNB/ NBPhCH₂Br F7 ROMP 55/45 2.08 — — 25.65 53.03 HexNB/NBPhCH₂Br

Table 3 provides a comparison of a quarternarized addition polymer P3I(HexNB/NBPhCH₂Br) to a quarternarized ROMP polymer system P4 where IonConductivity (IC) can be made equivalent. The addition polymer (AP) filmwas treated treated with N¹,N¹,N³,N³,2,2-hexamethylpropane-1,3-diamineand trimethylamine to give a crosslinked film with an IC value of 70.6at 60° C. The 100% solids polymerized polymerized ROMP systemcrosslinked using 1,1′-(1,4-phenylene)bis(N,N-dimethylmethanamine) (P4)was similarly treated with trimethylamine to give a crosslinked filmexhibiting an IC value of 53.03 at 60° C. The The IC of the additionpolymer is the same or better than the ROMP polymer. While it is is onlya single comparison, we believe it is indicative in general additionpolymers can can yield IC's as high as reported by Coates without givingup the other benefits of addition polymerization.

TABLE 4 Sample Polymer ID Composition Modulus Strength Elongation F147.5/52.5 — — — HexNB/NBEtBr F2 55/45  15 0.4 9.7 HexNB/NBBuBr F3 55/45297 5.6 2.2 HexNB/NBBuBr F4 55/45 173 8.1 7.7 HexNB/NBBuBr P4 55/45 — —— HexNB/NBPhCH₂Br F7 55/45 — — — HexNB/NBPhCH₂Br

By now it should be realized that a variety of methods for makingpolymeric materials have been disclosed, where such polymeric materialsare useful for forming membranes that are additionally useful forforming membranes that can be employed in forming an Alkali Fuel Cellthat addresses the issues with previously known AFCs. For example, it isbelieved that an AFC that encompasses an AAEM made using a polymerembodiment in accordance with the present disclosure will be long-livedand resistant to being blocked or destroyed by carbonate formation asdiscussed above. Further it is believe that AAEMs made from the fullysaturated polymer embodiments of the present disclosure will be moreoxidatively stable than any AAEM made from an unsaturated polymer.

Additionally, it should be realized that the polymer embodiments inaccordance with the present disclosure are also useful for formingelements of an AFC other than the the AAEM. For example, referring toparagraphs [0028] through [0039] in US Patent Application No.2007/0128500, which is incorporated herein by reference in its entirety,entirety, it is disclosed that electrodes 2 and 4 of FIG. 2 encompassesactive layers, respectively, and that each of such active layers 2a and4a encompass an element conducting hydroxide ions. It is believed thatsome of the polymer embodiments in accordance with the presentdisclosure would be useful in forming this element of active activeportions 2a and 4a.

1. A vinyl addition norbornene-type polymer comprising: a first type ofrepeating unit derived from a norbornene-type monomer represented byFormula A:

where for Formula A, m is from 0 to 3, at least one of R₉, R₁₀, R₁₁ andR₁₂ is a functional group (FG) characterized by being capable ofquaternization and the others are independently a hydrogen, a C₁ to C₅alkyl, an aryl or an alkyl-aryl group; and a second type of repeatingunit derived from a norbornene-type monomer represented by Formula B:

where for Formula B, m is as defined above and at least one of R₁₃, R₁₄,R₁₅ and R₁₆ is a substituted or unsubstituted maleimide-alkyl pendentgroup where the alkyl is a C₁ to C₆ alkyl or another cross-linkablegroup, and the others are independently
 2. The vinyl additionnorbornene-type polymer of claim 1, where the functional group of thefirst type of repeating unit is quaternized to comprise N⁺(CH₃)₃OH⁻. 3.A ROMP norbornene-type polymer comprising: a first type of repeatingunit derived from a norbornene-type monomer represented by Formula I:

where for Formula I, m is from 0 to 3, at least one of R₁, R₂, R₃ and R₄is the pendent group represented by Formula III:

where for Formula III, R′ is selected from —(CH₂)_(p)—, where p is from0 to 12; Ar is an aromatic group having one or more aromatic rings; R″is selected from —(CH₂)_(p)— where p is from 0 to 12, or—(CH₂)_(s)—O—(CH₂)_(t)—, where s and t are independently from 1 to 6,and R″ is coupled to the nitrogen of the quaternary ammonium functionalgroup by a covalent bond, each of R_(a), R_(b) and R_(c) areindependently selected from a methyl, an aryl or alkyl-aryl group wherethe alkyl is a C₁ to C₄ alkyl, and v is either 1 or 2, the others of R₁,R₂, R₃ and R₄ independently being a hydrogen, a C₁ to C₁₀ alkyl, an arylor an alkyl-aryl group; and a second type of repeating unit derived froma norbornene-type monomer represented by Formula II:

where for Formula H, m is as defined above and at least one of R₅, R₆,R₇ and R₈ is selected from a substituted or unsubstitutedmaleimide-alkyl pendent group where the alkyl is a C₁ to C₆ alkyl orNBCH₂OCH₂NB, NBCH₂(OCH₂CH₂)₂OCH₂NB, NBCH₂(OCH₂CH₂)₃OCH₂NB-, NB-NB,NB-Et-NB NB-Bu-NB, NB-Hx-NB, NBC₆H₄NB and NBCH₂C₆H₄CH₂NB, the others ofR₅, R₆, R₇ and R₈ being independently selected from a hydrogen, a C₁ toC₁₂ alkyl or terminally halogenated alkyl, an alkyl-aryl where the arylportion is optionally halogenated and the alkyl is C₁ to C₁₂ or a methylglycol ether —CH₂—(OCH₂CH₂)_(q)—OMe where q is from 1 to 4, with theproviso that cyclopentadiene and cyclooctene are not crosslinkermoieties.
 4. A hydroxide conducting anionic alkali exchange membranecomprising the vinyl addition polymer of claim
 2. 5. A hydroxideconducting anionic alkali exchange membrane comprising the ROMP polymerof claim
 3. 6. An alkali fuel cell comprising the hydroxide conductinganionic alkali exchange membrane of claim 4 or
 5. 7. An alkali fuel cellcomprising a first electrode having an active layer, where said activelayer comprises the polymer of claim 2 or claim
 4. 8. An alkali fuelcell comprising the hydroxide conducting anionic alkali exchangemembrane of claim 4 and a first electrode having an active layer wheresuch active layer comprises the vinyl addition polymer of claim
 2. 9. Analkali fuel cell comprising the hydroxide conducting anionic alkaliexchange membrane of claim 5 and a first electrode having an activelayer where such active layer comprises the vinyl addition polymer ofclaim
 2. 10. An alkali fuel cell comprising the hydroxide conductinganionic alkali exchange membrane of claim 5 and a first electrode havingan active layer where such active layer comprises the vinyl additionpolymer of claim 3.